Synthetic porous crystalline mcm-49, its synthesis and use

ABSTRACT

This invention relates to a new synthetic porous crystalline material, a method for its preparation and use thereof in catalytic conversion of organic compounds. The new crystalline material exhibits a distinctive X-ray diffraction pattern.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of U.S. application Ser. No. 07/717,436,filed Jun. 19, 1991.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a novel composition of synthetic porouscrystalline material, to a method for its preparation and to its use incatalytic conversion of organic compounds.

2. Description of the Prior Art

Zeolitic materials, both natural and synthetic, have been demonstratedin the past to have catalytic properties for various types ofhydrocarbon conversion. Certain zeolitic materials are ordered, porouscrystalline aluminosilicates having a definite crystalline structure asdetermined by X-ray diffraction, within which there are a large numberof smaller cavities which may be interconnected by a number of stillsmaller channels or pores. These cavities and pores are uniform in sizewithin a specific zeolitic material. Since the dimensions of these poresare such as to accept for adsorption molecules of certain dimensionswhile rejecting those of larger dimensions, these materials have come tobe known as "molecular sieves" and are utilized in a variety of ways totake advantage of these properties.

Such molecular sieves, both natural and synthetic, include a widevariety of positive ion-containing crystalline silicates. Thesesilicates can be described as a rigid three-dimensional framework ofSiO₄ and Periodic Table Group IIIA element oxide, e.g. AlO₄, in whichthe tetrahedra are cross-linked by the sharing of oxygen atoms wherebythe ratio of the total Group IIIA element, e.g. aluminum, and siliconatoms to oxygen atoms is 1:2. The electrovalence of the tetrahedracontaining the Group IIIA element, e.g. aluminum, is balanced by theinclusion in the crystal of a cation, for example an alkali metal or analkaline earth metal cation. This can be expressed wherein the ratio ofthe Group IIIA element, e.g. aluminum, to the number of various cations,such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of cationmay be exchanged either entirely or partially with another type ofcation utilizing ion exchange techniques in a conventional manner. Bymeans of such cation exchange, it has been possible to vary theproperties of a given silicate by suitable selection of the cation. Thespaces between the tetrahedra are occupied by molecules of water priorto dehydration.

Prior art techniques have resulted in the formation of a great varietyof synthetic zeolites. Many of these zeolites have come to be designatedby letter or other convenient symbols, as illustrated by zeolite A (U.S.Pat. No. 2,882,243); zeolite X (U.S. Pat. No. 2,882,244); zeolite Y(U.S. Pat. No. 3,130,007); zeolite ZK-5 (U.S. Pat. No. 3,247,195);zeolite ZK-4 (U.S. Pat. No. 3,314,752); zeolite ZSM-5 (U.S. Pat. No.3,702,886); zeolite ZSM-11 (U.S. Pat. No. 3,709,979); zeolite ZSM-12(U.S. Pat. No. 3,832,449), zeolite ZSM-20 (U.S. Pat. No. 3,972,983);ZSM-35 (U.S. Patent 4,016,245); zeolite ZSM-23 (U.S. Pat. No.4,076,842); zeolite MCM-22 (U.S. Pat. No. 4,954,325); and zeolite MCM-35(U.S. Pat. No. 4,981,663), merely to name a few.

The SiO₂ /Al₂ O₃ ratio of a given zeolite is often variable. Forexample, zeolite X can be synthesized with SiO₂ /Al₂ O₃ ratios of from 2to 3; zeolite Y, from 3 to about 6. In some zeolites, the upper limit ofthe SiO₂ /Al₂ O₃ ratio is unbounded. ZSM-5 is one such example whereinthe SiO₂ /Al₂ O₃ ratio is at least 5 and up to the limits of presentanalytical measurement techniques. U.S. Pat. No. 3,941,871 (Re. 29,948)discloses a porous crystalline silicate made from a reaction mixturecontaining no deliberately added alumina in the recipe and exhibitingthe X-ray diffraction pattern characteristic of ZSM-5. U.S. Pat. Nos.4,061,724, 4,073,865 and 4,104,294 describe crystalline silicate ofvarying alumina and metal content.

U.S. Pat. No. 4,439,409 refers to a composition of matter named PSH-3and its synthesis from a reaction mixture containing hexamethyleneimine,an organic compound which acts as directing agent for synthesis of thepresent MCM-49. A composition of matter appearing to be identical to thePSH-3 of U.S. Pat. No. 4,439,409, but with additional structuralcomponents, is taught in European Patent Application 293,032.Hexamethyleneimine is also used for synthesis of MCM-22 in U.S. Pat. No.4,954,325; MCM-35 in U.S. Pat. No. 4,981,663; and a ZSM-12 material inU.S. Patent 5,021,141. A composition of matter referred to as zeoliteSSZ-25 is taught in U.S. Pat. No. 4,826,667 and European PatentApplication 231,860, said zeolite being synthesized from a reactionmixture containing an adamantane quaternary ammonium ion.

SUMMARY OF THE INVENTION

The present invention is directed to a novel composition of a porouscrystalline material, named MCM-49, a method for its preparation, andthe conversion of organic compounds contacted with an active formthereof. The calcined form of the porous crystalline material of thisinvention transforms to a material not readily distinguishable fromcalcined crystalline material MCM-22 described in U.S. Pat. No.4,954,325. The instant crystalline material does not appear to containall the components apparently present in the PSH-3 composition describedin U.S. Pat. No. 4,439,409 The composition of this invention is notcontaminated with ZSM-12 or ZSM-5. The calcination transformationproduct exhibits unusual sorption capacities and unique catalyticutility when compared to PSH-3 synthesized in accordance with U.S. Pat.No. 4,439,409. It exhibits unique catalytic utility when compared toMCM-22 synthesized as taught in U.S. Pat. No. 4,954,325.

DESCRIPTION OF DRAWINGS

FIG. 1a shows a segment of the X-ray diffraction pattern of theas-synthesized precursor of MCM-22 from a repeat of Example 1 of U.S.Pat. No. 4,954,325.

FIG. 1b shows a segment of the X-ray diffraction pattern of theas-synthesized crystalline material product of Example 7, hereinafterpresented.

FIG. 1c shows a segment of the X-ray diffraction pattern of the calcinedMCM-22 from a repeat of Example 1 of U.S. Pat. No. 4,954,325.

FIGS. 2-7 are X-ray diffraction patterns of the as-synthesizedcrystalline material products of Examples 1, 3, 5, 7, 8, and 11,respectively, hereinafter presented.

DESCRIPTION OF SPECIFIC EMBODIMENTS

The crystalline material of this invention has a composition involvingthe molar relationship:

    X.sub.2 O.sub.3 :(n)YO.sub.2,

wherein X is a trivalent element, such as aluminum, boron, iron and/orgallium, preferably aluminum; Y is a tetravalent element such as siliconand/or germanium, preferably silicon; and n is less than about 35, e.g.from 2 to less than about 35, usually from about 10 to less than about35, more usually from about 15 to about 31. In the as-synthesized form,the material has a formula, on an anhydrous basis and in terms of molesof oxides per n moles of YO₂, as follows:

    (0.1-0.6)M.sub.2 O:(1-4)R:X.sub.2 O.sub.3 :nYO.sub.2

wherein M is an alkali or alkaline earth metal, and R is an organicmoiety. The M and R components are associated with the material as aresult of their presence during crystallization, and are easily removedby post-crystallization methods hereinafter more particularly described.

The crystalline material of the invention is thermally stable and in thecalcined form exhibits high surface area (greater than 400 m² /gm) andunusually large sorption capacity when compared to previously describedmaterials such as calcined PSH-3 and SSZ-25 having similar X-raydiffraction patterns. To the extent desired, the original sodium cationsof the as-synthesized material can be replaced in accordance withtechniques well known in the art, at least in part, by ion exchange withother cations. Preferred replacing cations include metal ions, hydrogenions, hydrogen precursor, e.g. ammonium, ions and mixtures thereof.Particularly preferred cations are those which tailor the catalyticactivity for certain hydrocarbon conversion reactions. These includehydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB,IIB, IIIB, IVB and VIII of the Periodic Table of the Elements.

In the as-synthesized form, the crystalline MCM-49 material of theinvention appears to be a single crystalline phase. It can be preparedin essentially pure form with little or no detectable impurity crystalphases and has an X-ray diffraction pattern which is distinguished fromthe patterns of other known as-synthesized or thermally treatedcrystalline materials by the lines listed in Table I below:

                  TABLE I                                                         ______________________________________                                        Interplanar d-Spacing (A)                                                                    Relative Intensity, I/Io × 100                           ______________________________________                                        13.15 ± 0.26                                                                               w-s*                                                          12.49 ± 0.24                                                                              vs                                                             11.19 ± 0.22                                                                              m-s                                                            6.43 ± 0.12 w                                                              4.98 ± 0.10 w                                                              4.69 ± 0.09 w                                                              3.44 ± 0.07 vs                                                             3.24 ± 0.06 w                                                              ______________________________________                                         *shoulder                                                                

The X-ray diffraction peak at 13.15±0.26 Angstrom Units (A) is usuallynot fully resolved for MCM-49 from the intense peak at 12.49±0.24, andis observed as a shoulder of this intense peak. For this reason, theprecise intensity and position of the 13.15±0.26 Angstroms peak aredifficult to determine within the stated range.

In its calcined form, the crystalline MCM-49 material of the inventiontransforms to a single crystal phase with little or no detectableimpurity crystal phases having an X-ray diffraction pattern which is notreadily distinguished from that of MCM-22, but distinguishable from thepatterns of other known crystalline materials. The X-ray diffractionpattern of the calcined form of MCM-49 includes the lines listed inTable II below:

                  TABLE II                                                        ______________________________________                                        Interplanar d-Spacing (A)                                                                    Relative Intensity, I/Io × 100                           ______________________________________                                        12.41 ± 0.24                                                                              vs                                                             11.10 ± 0.22                                                                              s                                                              8.89 ± 0.17 m-s                                                            6.89 ± 0.13 w                                                              6.19 ± 0.12 m                                                              6.01 ± 0.12 w                                                              5.56 ± 0.11 w                                                              4.96 ± 0.10 w                                                              4.67 ± 0.09 w                                                              4.59 ± 0.09 w                                                              4.39 ± 0.09 w                                                              4.12 ± 0.08 w                                                              4.07 ± 0.08 w-m                                                            3.92 ± 0.08 w-m                                                            3.75 ± 0.07 w-m                                                            3.57 ± 0.07 w                                                              3.43 ± 0.07  s-vs                                                          3.31 ± 0.06 w                                                              3.21 ± 0.06 w                                                              3.12 ± 0.06 w                                                              3.07 ± 0.06 w                                                              2.83 ± 0.05 w                                                              2.78 ± 0.05 w                                                              2.69 ± 0.05 w                                                              2.47 ± 0.05 w                                                              2.42 ± 0.05 w                                                              2.38 ± 0.05 w                                                              ______________________________________                                    

These X-ray diffraction data were collected with a Scintag diffractionsystem, equipped with a germanium solid state detector, using copperK-alpha radiation. The diffraction data were recorded by step-scanningat 0.02 degrees of two-theta, where theta is the Bragg angle, and acounting time of 10 seconds for each step. The interplanar spacings,d's, were calculated in Angstrom units (A), and the relative intensitiesof the lines, I/I_(o) is one-hundredth of the intensity of the strongestline, above background, were derived with the use of a profile fittingroutine (or second derivative algorithm). The intensities areuncorrected for Lorentz and polarization effects. The relativeintensities are given in terms of the symbols vs=very strong (60-100),s=strong (40-60), m=medium (20-40) and w=weak (0-20). It should beunderstood that diffraction data listed for this sample as single linesmay consist of multiple overlapping lines which under certainconditions, such as differences in crystallographic changes, may appearas resolved or partially resolved lines. Typically, crystallographicchanges can include minor changes in unit cell parameters and/or achange in crystal symmetry, without a change in the structure. Theseminor effects, including changes in relative intensities, can also occuras a result of differences in cation content, framework composition,nature and degree of pore filling, and thermal and/or hydrothermalhistory. Other changes in diffraction patterns can be indicative ofimportant differences between materials, which is the case for comparingMCM-49 with similar materials, e.g. MCM-22 and PSH-3.

The significance of differences in the X-ray diffraction patterns ofthese materials can be explained from a knowledge of the structures ofthe materials. MCM-22 and PSH-3 are members of an unusual family ofmaterials because, upon calcination, there are changes in the X-raydiffraction pattern that can be explained by a significant change in oneaxial dimension. This is indicative of a profound change in the bondingwithin the materials and not a simple loss of the organic material. Theprecursor members of this family can be clearly distinguished by X-raydiffraction from the calcined members. An examination of the X-raydiffraction patterns of both precursor and calcined forms shows a numberof reflections with very similar position and intensity, while otherpeaks are different. Some of these differences are directly related tothe changes in the axial dimension and bonding.

The present as-synthesized MCM-49 has an axial dimension similar tothose of the calcined members of the family and, hence, there aresimilarities in their X-ray diffraction patterns. Nevertheless, theMCM-49 axial dimension is different from that observed in the calcinedmaterials. For example, the changes in axial dimensions in MCM-22 can bedetermined from the positions of peaks particularly sensitive to thesechanges. Two such peaks occur at ˜13.5 Angstroms and ˜6.75 Angstroms inprecursor MCM-22, at ˜12.8 Angstroms and ˜6.4 Angstroms inas-synthesized MCM-49, and at ˜12.6 Angstroms and ˜6.30 Angstroms in thecalcined MCM-22. Unfortunately, the ˜12.8 Angstroms peak in MCM-49 isvery close to the intense ˜12.4 Angstroms peak observed for all threematerials, and is frequently not fully separated from it. Likewise, the˜12.6 Angstroms peak of the calcined MCM-22 material is usually onlyvisible as a shoulder on the intense ˜12.4 Angstroms peak. FIG. 1 showsthe same segment of the diffraction patterns of precursor MCM-22,calcined MCM-22, and MCM-49; the position of the ˜6.6-6.3 Angstroms peakis indicated in each segment by an asterisk. Because the ˜6.4 Angstromspeak is unobscured in MCM-49, it was chosen as a better means ofdistinguishing MCM-49 from the calcined forms of MCM-22 and PSH-3 ratherthan the much stronger ˜12.8 Angstroms peak. Table I lists alldiffraction peaks characteristic of MCM-49.

When used as a catalyst, the crystalline material of the invention maybe subjected to treatment to remove part or all of any organicconstituent. The crystalline material can also be used as a catalyst inintimate combination with a hydrogenating component such as tungsten,vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or anoble metal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponent can be in the composition by way of cocrystallization,exchanged into the composition to the extent a Group IIIA element, e.g.aluminum, is in the structure, impregnated therein or intimatelyphysically admixed therewith. Such component can be impregnated in or onto it such as, for example, by, in the case of platinum, treating thesilicate with a solution containing a platinum metal-containing ion.Thus, suitable platinum compounds for this purpose includechloroplatinic acid, platinous chloride and various compounds containingthe platinum amine complex.

The above crystalline MCM-49 material can be transformed to another formby thermal treatment. This thermal treatment is generally performed byheating at a temperature of at least about 370° C. for at least 1 minuteand generally not longer than 20 hours. While subatmospheric pressurecan be employed for the thermal treatment, atmospheric pressure isdesired for reasons of convenience. The thermal treatment can beperformed at a temperature up to about 925° C. The thermally treatedproduct, especially in its metal, hydrogen and ammonium forms, isparticularly useful in the catalysis of certain organic, e.g.hydrocarbon, conversion reactions. Non-limiting examples of suchreactions include those for which MCM-22 may be used as catalyst.Incorporated herein by reference for the descriptions of thoseparticular conversion reactions are U.S. Pat. Nos. 4,954,325; 4,973,784;4,992,611; 4,956,514; 4,962,250; 4,982,033; 4,962,257; 4,962,256;4,992,606; 4,954,663; 4,992,615; 4,983,276; 4,982,040; 4,962,239;4,968,402; 5,000,839; 5,001,296; 4,986,894; 5,001,295; 5,001,283;5,012,033; 5,019,670; 5,019,665; 5,019,664; and 5,013,422.

The crystalline material of this invention, when employed either as anadsorbent or as a catalyst in an organic compound conversion processshould be dehydrated, at least partially. This can be done by heating toa temperature in the range of 200° C. to about 370° C. in an atmospheresuch as air, nitrogen, etc. and at atmospheric, subatmospheric orsuperatmospheric pressures for between 30 minutes and 48 hours.Dehydration can also be performed at room temperature merely by placingthe MCM-49 in a vacuum, but a longer time is required to obtain asufficient amount of dehydration.

The present crystalline material can be prepared from a reaction mixturecontaining sources of alkali or alkaline earth metal (M), e.g. sodium orpotassium, cation, an oxide of trivalent element X, e.g. aluminum, anoxide of tetravalent element Y, e.g. silicon, directing agent (R), andwater, said reaction mixture having a composition, in terms of moleratios of oxides, within the following ranges:

    ______________________________________                                        Reactants      Useful       Preferred                                         ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                      12 to <35    18 to 31                                        H.sub.2 O/YO.sub.2                                                                             10 to 70     15 to 40                                        OH.sup.- /YO.sub.2                                                                           0.05 to 0.50 0.05 to 0.30                                      M/YO.sub.2     0.05 to 3.0  0.05 to 1.0                                       R/YO.sub.2      0.2 to 1.0   0.3 to 0.5                                       ______________________________________                                    

In this synthesis method, if more than one X component is present, atleast one must be present such that the YO₂ /X₂ O₃ molar ratio thereofis less than about 35. For example, if aluminum oxide and gallium oxidecomponents are used in the reaction mixture, at least one of the YO₂/Al₂ O₃ and YO₂ /Ga₂ O₃ molar ratios must be less than about 35. If onlyaluminum oxide has been added to the reaction mixture as a source of X,the YO₂ /Al₂ O₃ ratio must be less than about 35.

In the present synthesis method, the source of YO₂ must be comprisedpredominantly of solid YO₂, for example at least about 30 wt. % solidYO₂ in order to obtain the crystal product of the containing at leastabout 30 wt. % solid silica, e.g. Ultrasil (a precipitated, spray driedsilica containing about 90 wt. % silica) or HiSil (a precipitatedhydrated SiO₂ containing about 87 wt. % silica, about 6 wt. % free H₂ Oand about 4.5 wt. % bound H₂ O of hydration and having a particle sizeof about 0.02 micron) favors crystalline MCM-49 formation from the abovemixture. Preferably, therefore, the YO₂, e.g. silica, source contains atleast about 30 wt. % solid YO₂, e.g. silica, and more preferably atleast about 40 wt. % solid YO₂, e.g. silica.

Directing agent R is selected from the group consisting ofcycloalkylamine, azacycloalkane, diazacycloalkane, and mixtures thereof,alkyl comprising from 5 to 8 carbon atoms. Non-limiting examples of Rinclude cyclopentylamine, cyclohexylamine, cycloheptylamine,hexamethyleneimine, heptamethyleneimine, homopiperazine, andcombinations thereof.

Crystallization of the present crystalline material can be carried outat either static or stirred conditions in a suitable reactor vessel,such as for example, polypropylene jars or teflon lined or stainlesssteel autoclaves. The total useful range of temperatures forcrystallization is from about 80° C. to about 225° C. for a timesufficient for crystallization to occur at the temperature used, e.g.from about 24 hours to about 60 days. Thereafter, the crystals areseparated from the liquid and recovered.

It should be realized that the reaction mixture components can besupplied by more than one source. The reaction mixture can be preparedeither batchwise or continuously. Crystal size and crystallization timeof the new crystalline material will vary with the nature of thereaction mixture employed and the crystallization conditions.

Synthesis of the new crystals may be facilitated by the presence of atleast 0.01 percent, preferably 0.10 percent and still more preferably 1percent, seed crystals (based on total weight) of crystalline product.Useful seed crystals include MCM-22 and/or MCM-49.

The crystals prepared by the instant invention can be shaped into a widevariety of particle sizes. Generally speaking, the particles can be inthe form of a powder, a granule, or a molded product, such as anextrudate having particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the crystals can beextruded before drying or partially dried and then extruded.

The crystalline material of this invention can be used to catalyze awide variety of chemical conversion processes including many of presentcommercial/industrial importance. Examples of chemical conversionprocesses which are effectively catalyzed by the crystalline material ofthis invention, by itself or in combination with one or more othercatalytically active substances including other crystalline catalysts,include those requiring a catalyst with acid activity. Specific examplesinclude:

(1) alkylation of aromatic hydrocarbons, e.g. benzene, with long chainolefins, e.g. C₁₄ olefin, with reaction conditions including atemperature of from about 340° C. to about 500° C., a pressure of fromabout atmospheric to about 200 atmospheres, a weight hourly spacevelocity of from about 2 hr⁻¹ to about 2000 hr⁻¹ and an aromatichydrocarbon/olefin mole ratio of from about 1/1 to about 20/1, toprovide long chain alkyl aromatics which can be subsequently sulfonatedto provide synthetic detergents;

(2) alkylation of aromatic hydrocarbons with gaseous olefins to provideshort chain alkyl aromatic compounds, e.g. the alkylation of benzenewith propylene to provide cumene, with reaction conditions including atemperature of from about 10° C. to about 125° C., a pressure of fromabout 1 to about 30 atmospheres, and an aromatic hydrocarbon weighthourly space velocity (WHSV) of from 5 hr⁻¹ to about 50 hr⁻¹ ;

(3) alkylation of reformate containing substantial quantities of benzeneand toluene with fuel gas containing C₅ olefins to provide, inter alia,mono- and dialkylates with reaction conditions including a temperatureof from about 315° C. to about 455° C., a pressure of from about 400 toabout 800 psig, a WHSV-olefin of from about 0.4 hr⁻¹ to about 0.8 hr⁻¹,a WHSV-reformate of from about 1 hr to about 2 hr and a gas recycle offrom about 1.5 to 2.5 vol/vol fuel gas feed;

(4) alkylation of aromatic hydrocarbons, e.g. benzene, toluene, xyleneand naphthalene, with long chain olefins, e.g. C₁₄ olefin, to providealkylated aromatic lube base stocks with reaction conditions including atemperature of from about 160° C. to about 260° C. and a pressure offrom about 350 to 450 psig; and

(5) alkylation of phenols with olefins or equivalent alcohols to providelong chain alkyl phenols with reaction conditions including atemperature of from about 200° C. to about 250° C., a pressure of fromabout 200 to 300 psig and a total WHSV of from about 2 hr⁻¹ to about 10hr⁻¹.

In the case of many catalysts, it is desired to incorporate the newcrystal with another material resistant to the temperatures and otherconditions employed in organic conversion processes. Such materialsinclude active and inactive materials and synthetic or naturallyoccurring zeolites as well as inorganic materials such as clays, silicaand/or metal oxides such as alumina. The latter may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. Use of a material in conjunctionwith the new crystal, i.e. combined therewith or present duringsynthesis of the new crystal, which is active, tends to change theconversion and/or selectivity of the catalyst in certain organicconversion processes. Inactive materials suitably serve as diluents tocontrol the amount of conversion in a given process so that products canbe obtained economically and orderly without employing other means forcontrolling the rate of reaction. These materials may be incorporatedinto naturally occurring clays, e.g. bentonite and kaolin, to improvethe crush strength of the catalyst under commercial operatingconditions. Said materials, i.e. clays, oxides, etc., function asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in commercial use it is desirable to preventthe catalyst from breaking down into powder-like materials. These clayand/or oxide binders have been employed normally only for the purpose ofimproving the crush strength of the catalyst.

Naturally occurring clays which can be composited with the new crystalinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with the present crystal also includeinorganic oxides, notably alumina.

In addition to the foregoing materials, the new crystal can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided crystalline material andinorganic oxide matrix vary widely, with the crystal content rangingfrom about 1 to about 90 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 2 to about 80 weight percent of the composite.

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented. In theexamples, whenever sorption data are set forth for comparison ofsorptive capacities for water, cyclohexane and/or n-hexane, they wereEquilibrium Adsorption values determined as follows:

A weighed sample of the calcined adsorbant was contacted with thedesired pure adsorbate vapor in an adsorption chamber, evacuated to lessthan 1 mm and contacted with 12 Torr of water vapor and 40 Torr ofn-hexane or cyclohexane vapor, pressures less than the vapor-liquidequilibrium pressure of the respective adsorbate at 90° C. The pressurewas kept constant (within about ±0.5 mm) by addition of adsorbate vaporcontrolled by a manostat during the adsorption period, which did notexceed about 8 hours. As adsorbate was adsorbed by the new crystal, thedecrease in pressure caused the manostat to open a valve which admittedmore adsorbate vapor to the chamber to restore the above controlpressures. Sorption was complete when the pressure change was notsufficient to activate the manostat. The increase in weight wascalculated as the adsorption capacity of the sample in g/100 g ofcalcined adsorbant. The new synthetic material of this invention alwaysexhibits Equilibrium Adsorption values of greater than about 10 wt. %for water vapor, greater than about 4.3 wt. %, usually greater thanabout 7 wt. % for cyclohexane vapor and greater than about 10 wt. % forn-hexane vapor. These vapor sorption capacities are a notabledistinguishing feature of the present crystalline material.

When Alpha Value is examined, it is noted that the Alpha Value is anapproximate indication of the catalytic cracking activity of thecatalyst compared to a standard catalyst and it gives the relative rateconstant (rate of normal hexane conversion per volume of catalyst perunit time). It is based on the activity of silica-alumina crackingcatalyst taken as an Alpha of 1 (Rate Constant=0.016 sec⁻¹). The AlphaTest is described in U.S. Pat. No. 3,354,078; in the Journal ofCatalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p.395 (1980), each incorporated herein by reference as to thatdescription. The experimental conditions of the test used herein includea constant temperature of 538° C. and a variable flow rate as describedin detail in the Journal of Catalysis, Vol. 61, p. 395.

EXAMPLE 1

A 1 part quantity of Al₂ (SO₄)₃.xH₂ O was dissolved in a solutioncontaining 1.83 parts of 50% NaOH solution and 13 parts of H₂ O. To thiswere added 1.78 parts of hexamethyleneimine (HMI) followed by 6.6 partsof amorphous silica precursor (46% solids). The mixture was thoroughlymixed until uniform.

The reaction mixture had the following composition in mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           30                                                                  OH.sup.- /SiO.sub.2 =                                                                   0.25                                                                Na/SiO.sub.2 =                                                                          0.43                                                                HMI/SiO.sub.2 =                                                                         0.35                                                                H.sub.2 O/SiO.sub.2 =                                                                   19.4                                                         ______________________________________                                    

The mixture was crystallized in a stirred reactor at 150° C. for 4 days.The crystals were filtered, washed with water and dried at 120° C. Aportion of the product was submitted for X-ray analysis and identifiedas the new crystalline material MCM-49. The material exhibited the X-raypowder diffraction pattern as shown in Table III and FIG. 2.

The chemical composition of the product was, in wt. %:

    ______________________________________                                                N     1.81                                                                    Na    0.38                                                                    Al.sub.2 O.sub.3                                                                    7.1                                                                     SiO.sub.2                                                                           72.8                                                                    Ash   79.2                                                            ______________________________________                                    

The SiO₂ /Al₂ O₃ molar ratio of this product was 17.4.

The sorption capacities, after calcining for 6 hours at 538° C. were, inwt. %:

    ______________________________________                                        Cyclohexane, 40 Torr                                                                             4.4                                                        n-Hexane, 40 Torr  12.8                                                       H.sub.2 O, 12 Torr 11.1                                                       ______________________________________                                    

A portion of the sample was calcined in air for 16 hours at 538° C. Thismaterial exhibited the X-ray diffraction pattern shown in Table IV.

                  TABLE III                                                       ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        3.2           27.5       11                                                   6.75          13.09        36 sh                                              7.08          12.49      100                                                  7.88          11.23      40                                                   9.81          9.02       24                                                   12.79         6.92       13                                                   13.42         6.60        5*                                                  13.87         6.38       6                                                    14.24         6.22       7                                                    14.64         6.05       4                                                    15.24         5.81       2                                                    15.81         5.61       8                                                    17.72         5.01       2                                                    18.91         4.69       4                                                    19.27         4.61       5                                                    20.09         4.42       19                                                   20.83         4.26       6                                                    21.48         4.14       15                                                   21.78         4.08       29                                                   22.22         4.00       12                                                   22.59         3.94       36                                                   23.56         3.78       19                                                   24.87         3.58       21                                                   25.10         3.55       6                                                    25.89         3.44       80                                                   26.32         3.39       7                                                    26.81         3.33       17                                                   27.57         3.24       11                                                   28.36         3.15       7                                                    29.03         3.08       3                                                    29.50         3.03       2                                                    31.47         2.842      3                                                    32.16         2.784      3                                                    33.26         2.694      6                                                    34.08         2.631      2                                                    34.83         2.576      1                                                    36.25         2.478      2                                                    36.96         2.432      2                                                    37.72         2.385      7                                                    ______________________________________                                         sh = Shoulder                                                                 * = Impurity peak                                                        

                  TABLE IV                                                        ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        3.4           26.0       6                                                    6.96          12.69        45 sh                                              7.15          12.37      100                                                  7.97          11.09      58                                                   9.97          8.87       49                                                   12.88         6.88       10                                                   13.50         6.56        3*                                                  14.34         6.18       26                                                   14.76         6.00       8                                                    15.30         5.79       1                                                    15.96         5.55       13                                                   17.84         4.97       1                                                    19.03         4.66       3                                                    19.34         4.59       2                                                    19.67         4.51        2*                                                  20.26         4.38       10                                                   21.18         4.20       3                                                    21.59         4.12       10                                                   21.88         4.06       17                                                   22.40         3.97       8                                                    22.72         3.91       28                                                   23.74         3.75       16                                                   24.73         3.60       3                                                    24.98         3.57       10                                                   25.23         3.53       5                                                    26.00         3.43       57                                                   26.98         3.30       12                                                   27.81         3.21       12                                                   28.64         3.12       7                                                    29.14         3.06       2                                                    29.69         3.01       2                                                    31.62         2.830      3                                                    32.28         2.773      3                                                    33.38         2.685      6                                                    34.43         2.605      2                                                    34.98         2.565      2                                                    36.39         2.469      1                                                    37.09         2.424      2                                                    37.86         2.377      4                                                    ______________________________________                                         sh = Shoulder                                                                 *= Impurity peak                                                         

EXAMPLE 2

The calcined portion of the product of Example 1 was ammonium exchangedand calcined at 538° C. in air for 16 hours to provide the hydrogen formtransformation product of the crystalline MCM-49. The Alpha Test provedthis material to have an Alpha Value of 291.

EXAMPLE 3

A 1.45 part quantity of sodium aluminate was added to a solutioncontaining 1 part of 50% NaOH solution and 53.1 parts H₂ O. A 5.4 partquantity of HMI was added, followed by 10.3 parts of Ultrasil, aprecipitated spray-dried silica (about 90% SiO₂). The reaction mixturewas thoroughly mixed and transferred to a stainless steel autoclaveequipped with a stirrer.

The reaction mixture had the following composition in mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           25                                                                  OH.sup.- /SiO.sub.2 =                                                                   0.19                                                                Na/SiO.sub.2 =                                                                          0.19                                                                HMI/SiO.sub.2 =                                                                         0.35                                                                H.sub.2 O/SiO.sub.2 =                                                                   19.3                                                         ______________________________________                                    

The mixture was crystallized with stirring at 150° C. for 8 days. Theproduct was identified as poorly crystalline MCM-49 and had the X-raypattern which appears in Table V and FIG. 3.

The chemical composition of the product was, in wt. %:

    ______________________________________                                                N     2.29                                                                    Na    0.19                                                                    Al.sub.2 O.sub.3                                                                    6.3                                                                     SiO.sub.2                                                                           71.0                                                                    Ash   77.9                                                            ______________________________________                                    

The silica/alumina mole ratio of the product was 19.2.

The sorption capacitites, after calcining for 16 hours at 538° C. were,in wt. %:

    ______________________________________                                        Cyclohexane, 40 Torr                                                                             9.9                                                        n-Hexane, 40 Torr  14.6                                                       H.sub.2 O, 12 Torr 15.1                                                       ______________________________________                                    

A portion of the sample was calcined in air for 16 hours at 538° C. Thismaterial exhibited the X-ray diffraction pattern shown in Table VI.

                  TABLE V                                                         ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        3.0           29.3       8                                                    3.9           22.8        2+                                                  6.66          13.27      34                                                   7.10          12.45      100                                                  7.91          11.18      39                                                   9.24          9.57       16*                                                  9.79          9.04       23                                                   12.79         6.92       11                                                   13.60         6.51       5                                                    14.28         6.20       5                                                    14.68         6.03       5                                                    15.33         5.78       2                                                    15.83         5.60       7                                                    17.80         4.98       2                                                    18.94         4.68       3                                                    19.32         4.59       8                                                    20.09         4.42       21                                                   21.51         4.13       17                                                   21.82         4.07       27                                                   22.17         4.01       13                                                   22.58         3.94       33                                                   23.50         3.79       19                                                   24.09         3.69        8*                                                  24.96         3.57       23                                                   25.55         3.49       11*                                                  25.93         3.44       73                                                   26.82         3.32       20                                                   27.54         3.24       9                                                    28.32         3.15        9**                                                 29.07         3.07        5**                                                 31.50         2.840      3                                                    32.15         2.784      3                                                    33.31         2.690      6                                                    34.48         2.601      2                                                    36.26         2.478      2                                                    37.03         2.428      2                                                    37.75         2.383      6                                                    ______________________________________                                         += Noncrystallographic MCM49 peak                                             *= Impurity peak                                                              **= May contain impurity peak                                            

                  TABLE VI                                                        ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        3.9           22.8         6+                                                 6.88          12.84        46 sh                                              7.11          12.43      100                                                  7.97          11.10      57                                                   9.35          9.46        25*                                                 9.94          8.90       48                                                   12.53         7.07        4*                                                  12.82         6.90       13                                                   13.41         6.60        3*                                                  14.30         6.19       36                                                   14.73         6.01        6                                                   15.93         5.56       10                                                   17.90         4.96        2                                                   18.98         4.68        3                                                   19.34         4.59        3                                                   20.18         4.40       11                                                   21.56         4.12       11                                                   21.86         4.07       18                                                   22.34         3.98       10                                                   22.67         3.92       30                                                   23.68         3.76       17                                                   24.94         3.57       15                                                   25.20         3.53        6*                                                  25.97         3.43       60                                                   26.93         3.31       13                                                   27.79         3.21       11                                                   28.56         3.13         8**                                                29.10         3.07         3**                                                29.60         3.02        1                                                   31.58         2.83        3                                                   32.24         2.776       3                                                   33.34         2.688       7                                                   34.59         2.593       3                                                   36.33         2.473       1                                                   37.05         2.426       2                                                   37.79         2.380       4                                                   ______________________________________                                         sh  = Shoulder                                                                += Noncrystallographic MCM49 peak                                             *= Impurity peak                                                              **= May contain impurity peak                                            

EXAMPLE 4

The calcined portion of the product of Example 3 was ammonium exchangedand calcined at 538° C. in air for 16 hours to provide the hydrogen formtransformation product of the crystalline MCM-49. The Alpha Test provedthis material to have an Alpha Value of 286.

EXAMPLE 5

A 10.5 part quantity of gallium oxide was added to a solution containing1.0 part sodium aluminate, 3.05 parts 50% NaOH solution and 280 parts H₂O. A 25.6 part quantity of HMI was added followed by 56.6 parts ofUltrasil and 1.7 parts of MCM-22 seeds. The slurry was thoroughly mixed.

The composition of the reaction mixture in mole ratios:

    ______________________________________                                        SiO.sub.2 /Al.sub.2 O.sub.3 =                                                                 138                                                           SiO.sub.2 /Ga.sub.2 O.sub.3 =                                                                 17.9                                                          OH.sup.- /SiO.sub.2 =                                                                         0.057                                                         Na/SiO.sub.2 =  0.057                                                         HMI/SiO.sub.2 = 0.30                                                          H.sub.2 O/SiO.sub.2 =                                                                         18.4                                                          ______________________________________                                    

The mixture was crystallized with stirring at 150° C. for 10 days. Theproduct was identified as poorly crystalline MCM-49 and had the X-raypattern which appears in Table VII and FIG. 4.

The chemical composition of the product was, in wt. %:

    ______________________________________                                                N     1.89                                                                    Na    0.40                                                                    Ga    8.5                                                                     Al.sub.2 O.sub.3                                                                    0.81                                                                    SiO.sub.2                                                                           65.6                                                                    Ash   79.3                                                            ______________________________________                                    

with silica/alumina and silica/gallia molar ratios for the product of:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3                                                            138                                                                  SiO.sub.2 /Ga.sub.2 O.sub.3                                                            17.9                                                          ______________________________________                                    

The sorption capacities, after calcining for 3 hours at 538° C., in wt.%:

    ______________________________________                                        Cyclohexane, 40 Torr                                                                             13.3                                                       n-Hexane, 40 Torr  11.3                                                       H.sub.2 O, 12 Torr 12.3                                                       ______________________________________                                    

A portion of the sample was calcined in air for 16 hours at 538° C. Thismaterial exhibited the X-ray diffraction pattern shown in Table VIII.

                  TABLE VII                                                       ______________________________________                                        Degrees    Interplanar                                                        2-Theta    d-spacing (A)      I/I.sub.o                                       ______________________________________                                        3.9        22.8                6+                                             6.66       13.27               30 sh                                          7.08       12.48              100                                             7.92       11.17               43                                             9.27       9.54                8*                                             9.74       9.08                20                                             12.78      6.93                12                                             13.75      6.44                6                                              14.28      6.20                5                                              14.62      6.06                3                                              15.78      5.62                8                                              17.99      4.93                3                                              18.92      4.69                6                                              20.10      4.42                24                                             20.86      4.26                9                                              21.47      4.14                10                                             21.73      4.09                26                                             22.57      3.94                29                                             23.53      3.78                22                                             24.92      3.57                24                                             25.91      3.44                82                                             26.80      3.33                19                                             27.43      3.25                14                                             28.31      3.15                10                                             29.04      3.07                5                                              31.59      2.832               8                                              32.17      2.783               3                                              33.25      2.694               6                                              33.70      2.659               8*                                             35.12      2.555               4*                                             35.96      2.497               11*                                            36.29      2.476               4                                              37.73      2.384               7                                              ______________________________________                                         sh = Shoulder                                                                 + = Noncrystallographic MCM49 peak                                            * = Impurity peak                                                        

                  TABLE VIII                                                      ______________________________________                                        Degrees    Interplanar                                                        2-Theta    d-spacing (A)      I/I.sub.o                                       ______________________________________                                        3.9        22.8                11+                                            6.89       12.83               40 sh                                          7.11       12.43              100                                             7.96       11.11               55                                             9.40       9.41                10*                                            9.94       8.90                47                                             12.81      6.91                10                                             14.31      6.19                32                                             14.74      6.01                4                                              15.94      5.56                12                                             17.89      4.96               <1                                              19.00      4.67                3                                              19.39      4.58                3                                              20.22      4.39                9                                              21.56      4.12                9                                              21.86      4.07                17                                             22.70      3.92                29                                             23.70      3.75                16                                             24.99      3.56                14                                             26.01      3.43                57                                             26.96      3.31                12                                             27.84      3.20                10                                             28.60      3.12                5                                              29.10      3.07                3                                              31.63      2.829               6                                              32.28      2.773               3                                              33.39      2.684               7                                              33.72      2.658               9*                                             35.07      2.559               4*                                             35.94      2.499               4*                                             36.40      2.468               1                                              37.13      2.422               2                                              37.88      2.375               3                                              ______________________________________                                         sh = Shoulder                                                                 + = Noncrystallographic MCM49 peak                                            * = Impurity peak                                                        

EXAMPLE 6

The calcined portion of the product of Example 5 was ammonium exchangedand calcined at 538° C. in air for 16 hours to provide the hydrogen formtransformation product of the crystalline MCM-49. The Alpha Test provedthis material to have an Alpha Value of 64.

EXAMPLE 7

A solution containing 1 part of Al₂ (SO₄)₃.xH₂ O, 1.31 parts of 50% NaOHsolution and 14.0 parts of H₂ O was prepared. To this were added 2.8parts of Ultrasil precipitated silica followed by 1.48 parts of HMI. Thereaction mixture was thoroughly mixed. The composition of the reactionmixture in mole ratios was:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           25.5                                                                OH.sup.- /SiO.sub.2 =                                                                   0.15                                                                Na/SiO.sub.2 =                                                                          0.39                                                                HMI/SiO.sub.2 =                                                                         0.35                                                                H.sub.2 O/SiO.sub.2 =                                                                   19.4                                                         ______________________________________                                    

The mixture was crystallized for 5 days at 143° C. The product waswashed, dried at 120° C. and identified by X-ray analysis as MCM-49. Itexhibited an X-ray pattern as shown in Table IX and FIG. 5.

The sorption capacities, after calcining for 16 hours at 538° C. were,in wt. %:

    ______________________________________                                        Cyclohexane, 40 Torr                                                                             8.8                                                        n-Hexane, 40 Torr  15.9                                                       H.sub.2 O, 12 Torr 13.6                                                       ______________________________________                                    

The chemical composition of the product was, in wt. %:

    ______________________________________                                                N     1.83                                                                    Na    0.27                                                                    Al.sub.2 O.sub.3                                                                    6.8                                                                     SiO.sub.2                                                                           73.8                                                                    Ash   80.5                                                            ______________________________________                                    

The silica/alumina mole ratio of the product was 18.4.

The surface area of this material was measured to be 459 m² /g.

A portion of the sample was calcined in air for 16 hours at 538° C. Thismaterial exhibited the X-ray diffraction pattern shown in Table X.

                  TABLE IX                                                        ______________________________________                                        Degrees    Interplanar                                                        2-Theta    d-spacing (A)      I/I.sub.o                                       ______________________________________                                        3.1        28.5                17                                             4.0        22.2                3+                                             6.73       13.14               43 sh                                          7.08       12.48              100                                             7.92       11.16               42                                             9.69       9.13                23                                             12.80      6.91                13                                             13.76      6.44                7                                              14.27      6.20                6                                              14.65      6.05                3                                              15.85      5.59                7                                              17.82      4.98                2                                              18.92      4.69                3                                              19.32      4.59                8                                              20.13      4.41                20                                             21.48      4.14                12                                             21.82      4.07                31                                             22.56      3.94                36                                             23.59      3.77                18                                             24.91      3.57                22                                             25.91      3.44                79                                             26.74      3.33                20                                             27.61      3.23                7                                              28.25      3.16                8                                              29.14      3.06                3                                              31.48      2.842               3                                              32.16      2.783               3                                              33.26      2.694               6                                              33.85      2.648               3 sh                                           34.72      2.584               2                                              36.26      2.478               2                                              37.00      2.429               2                                              37.73      2.384               7                                              ______________________________________                                         sh = Shoulder                                                                 + = Noncrystallographic MCM49 peak                                       

                  TABLE X                                                         ______________________________________                                        Degrees    Interplanar                                                        2-Theta    d-spacing (A)      I/I.sub.o                                       ______________________________________                                        3.9        22.8                6+                                             6.91       12.79               38 sh                                          7.12       12.42              100                                             7.96       11.10               53                                             9.94       8.90                39                                             12.84      6.90                11                                             14.30      6.19                39                                             14.71      6.02                10                                             15.92      5.57                12                                             18.00      4.93                1                                              18.98      4.67                3                                              19.34      4.59                3                                              20.17      4.40                10                                             21.55      4.12                10                                             21.86      4.07                17                                             22.67      3.92                27                                             23.69      3.75                15                                             24.96      3.57                13                                             25.98      3.43                61                                             26.93      3.31                13                                             27.80      3.21                9                                              28.58      3.12                6                                              29.11      3.07                2                                              29.63      3.02                1                                              31.57      2.834               3                                              32.23      2.777               3                                              33.35      2.687               6                                              34.60      2.593               3                                              36.34      2.472               1                                              37.06      2.426               1                                              37.83      2.378               5                                              ______________________________________                                         sh = Shoulder                                                                 + = Noncrystallographic MCM49 peak                                       

EXAMPLE 8

A 2.24 part quantity of 45% sodium aluminate was added to a solutioncontaining 1.0 part of 50% NaOH solution and 43.0 parts H₂ O in anautoclave. An 8.57 part quantity of Ultrasil precipitated silica wasadded with agitation, followed by 4.51 parts of HMI.

The reaction mixture had the following composition, in mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           23                                                                  OH.sup.- /SiO.sub.2 =                                                                   0.21                                                                Na/SiO.sub.2 =                                                                          0.21                                                                HMI/SiO.sub.2 =                                                                         0.35                                                                H.sub.2 O/SiO.sub.2 =                                                                   19.3                                                         ______________________________________                                    

The mixture was crystallized at 150° C. for 84 hours with stirring. Theproduct was identified as MCM-49 and had the X-ray pattern which appearsin Table XI and FIG. 6.

The chemical composition of the product was, in wt. %:

    ______________________________________                                                N     1.70                                                                    Na    0.70                                                                    Al.sub.2 O.sub.3                                                                    7.3                                                                     SiO.sub.2                                                                           74.5                                                                    Ash   84.2                                                            ______________________________________                                    

The silica/alumina mole ratio of the product was 17.3.

The sorption capacities, after calcining at 538° C. for 9 hours were, inwt. %:

    ______________________________________                                        Cyclohexane, 40 Torr                                                                             10.0                                                       n-Hexane, 40 Torr  13.1                                                       H.sub.2 O, 12 Torr 15.4                                                       ______________________________________                                    

A portion of the sample was calcined in air for 3 hours at 538° C.. Thismaterial exhibited the X-ray diffraction pattern shown in Table XII.

                  TABLE XI                                                        ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        3.1           28.5       18                                                   3.9           22.8         7+                                                 6.81          12.99        61 sh                                              7.04          12.55      97                                                   7.89          11.21      41                                                   9.80          9.03       40                                                   12.76         6.94       17                                                   13.42         6.60        4*                                                  13.92         6.36       17                                                   14.22         6.23       11                                                   14.63         6.05        2                                                   15.81         5.61       15                                                   17.71         5.01        4                                                   18.86         4.71        4                                                   19.23         4.62        6                                                   20.09         4.42       27                                                   20.93         4.24        8                                                   21.44         4.14       17                                                   21.74         4.09       37                                                   22.16         4.01       17                                                   22.56         3.94       58                                                   23.53         3.78       26                                                   24.83         3.59       22                                                   25.08         3.55       10                                                   25.86         3.45       100                                                  26.80         3.33       28                                                   27.53         3.24       21                                                   28.33         3.15       15                                                   28.98         3.08        4                                                   29.47         3.03        2                                                   31.46         2.843       4                                                   32.08         2.790       6                                                   33.19         2.699       9                                                   34.05         2.633       5                                                   34.77         2.580       4                                                   36.21         2.481       2                                                   36.90         2.436       3                                                   37.68         2.387       8                                                   ______________________________________                                         sh = Shoulder                                                                 += Noncrystallographic MCM49 peak                                             *= Impurity peak                                                         

                  TABLE XII                                                       ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        3.2           28.0         9+                                                 3.9           22.8         7+                                                 6.90          12.81        48 sh                                              7.13          12.39      100                                                  7.98          11.08      46                                                   9.95          8.89       53                                                   12.87         6.88       10                                                   14.32         6.18       36                                                   14.74         6.01       11                                                   15.94         5.56       17                                                   17.87         4.96        2                                                   19.00         4.67        5                                                   19.35         4.59        3                                                   20.24         4.39       14                                                   21.06         4.22        5                                                   21.56         4.12       15                                                   21.87         4.06       25                                                   22.32         3.98       12                                                   22.69         3.92       41                                                   23.69         3.76       23                                                   24.95         3.57       19                                                   25.22         3.53        4                                                   25.99         3.43       90                                                   26.94         3.31       20                                                   27.73         3.22       17                                                   28.55         3.13       11                                                   29.11         3.07        3                                                   29.63         3.01        2                                                   31.59         2.833       6                                                   32.23         2.777       4                                                   33.34         2.687       9                                                   34.35         2.611       4                                                   34.92         2.570       3                                                   36.35         2.471       2                                                   37.07         2.425       2                                                   37.82         2.379       6                                                   ______________________________________                                         sh = Shoulder                                                                 += Noncrystallographic MCM49 peak                                        

EXAMPLE 9

The calcined portion of the product of Example 8 was ammonium exchangedand calcined at 538° C. in air for 3 hours to provide the hydrogen formtransformation product of the crystalline MCM-49. The Alpha Test provedthis material to have an Alpha Value of 308.

EXAMPLE 10

In two separate experiments, propylene was passed into a reactorcontaining catalyst at 538° C., 1 atmosphere pressure, ahelium/hydrocarbon ratio of 1.1 and a weight hourly space velocity of3.10 hr⁻¹. The catalyst of the first experiment was hydrogen-form MCM-22prepared as in Example 1 of U.S. Pat. No. 4,954,325 (hereinafter Example12). The catalyst of the second experiment was the Example 6 product.After 20 minutes on stream, the product distribution, in weight percent,was determined to be as shown in Table XIII. Significant propylenearomatization selectivity to benzene is observed for the Example 6catalyst compared to MCM-22. The benzene yield over the Example 6catalyst was 7.16 wt. %, compared to 2.64 wt. % for MCM-22.

                  TABLE XIII                                                      ______________________________________                                        PROPYLENE AROMATIZATION                                                       Catalyst         MCM-22   Example 6                                           ______________________________________                                        Product Dist., wt. %                                                          C.sub.1          0.35     1.28                                                C.sub.2 ═    1.59     8.72                                                C.sub.2          12.82    0.00                                                C.sub.3 + C.sub.3.sup.═                                                                    34.58    41.87                                               Iso-C.sub.4      9.28     2.73                                                N--C.sub.4       2.65     0.00                                                Iso + 1-C.sub.4 ═                                                                          4.58     5.51                                                C--C.sub.4 ═ 1.72     2.31                                                T--C.sub.4 ═ 2.49     1.82                                                N--C.sub.5       0.24     0.10                                                Cyclo-C.sub.5    0.59     0.19                                                Iso-C.sub.5      2.27     0.93                                                C.sub.5 ═    2.25     2.94                                                C.sub.6 Par.     1.04     0.52                                                C.sub.6 ═    0.18     0.22                                                C.sub.7 Par. + OL.                                                                             0.22     0.12                                                C.sub.8 -C.sub.12 Par. + OL.                                                                   0.00     0.00                                                C.sub.13 + Par. + OL.                                                                          0.00     0.00                                                Benzene          2.64     7.16                                                Toluene          9.08     8.10                                                C.sub.8 Ar.      7.52     6.78                                                C.sub.9 Ar.      3.01     3.87                                                C.sub.10 -C.sub.11 Ar.                                                                         0.29     0.91                                                C.sub.12 + Ar.   0.00     0.00                                                Naphthalene      0.38     0.77                                                M-Naphthalenes   0.26     3.16                                                ______________________________________                                    

EXAMPLE 11

Sodium aluminate comprising 40 wt. % Al₂ O₃, 33 wt. % Na₂ O, and 27 wt.% H₂ O was added to a solution containing NaOH and H₂ O in an autoclave.Ultrasil precipitated silica was then added with agitation, followed byaminocyclcoheptane (R) directing agent to form a reaction mixture.

This mixture had the following composition, in mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           33.34                                                               OH.sup.- /SiO.sub.2 =                                                                   0.18                                                                Na/SiO.sub.2 =                                                                          0.18                                                                R/SiO.sub.2 =                                                                           0.35                                                                H.sub.2 O/SiO.sub.2 =                                                                   18.83                                                        ______________________________________                                    

The mixture was crystallized at 143° C. for 192 hours with stirring. Theproduct was identified as MCM-49 and had the X-ray pattern which appearsin Table XIV and FIG. 7.

The chemical composition of the product was, in wt. %:

    ______________________________________                                                N     1.51                                                                    Na    0.83                                                                    Al.sub.2 O.sub.3                                                                    4.6                                                                     SiO.sub.2                                                                           74.2                                                                    Ash   79.2                                                            ______________________________________                                    

The silica/alumina mole ratio of the product was 27.4.

The sorption capacities, after calcining at 538° C. for 9 hours were, inwt. %:

    ______________________________________                                        Cyclohexane, 40 Torr                                                                             7.5                                                        n-Hexane, 40 Torr  14.0                                                       H.sub.2 O, 12 Torr 13.5                                                       ______________________________________                                    

                  TABLE XIV                                                       ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        4.1           21.4        1                                                   6.87          12.87      41                                                   7.14          12.38      100                                                  7.98          11.09      26                                                   9.88          8.95       18                                                   12.85         6.89       14                                                   14.00         6.33       10                                                   14.31         6.19       11                                                   14.74         6.01        2                                                   15.88         5.58       13                                                   17.79         4.99        4                                                   18.95         4.68        6                                                   19.34         4.59        7                                                   20.20         4.40       18                                                   21.06         4.22        7                                                   21.51         4.13       12                                                   21.82         4.07       27                                                   22.63         3.93       46                                                   23.60         3.77       19                                                   24.90         3.58       25                                                   25.14         3.54        7                                                   25.92         3.44       90                                                   26.82         3.32       26                                                   27.66         3.22       13                                                   28.43         3.14       12                                                   29.03         3.08        4                                                   29.45         3.03        3                                                   31.51         2.839       4                                                   32.15         2.784       5                                                   33.24         2.695       8                                                   34.13         2.627       4                                                   34.84         2.575       2                                                   36.26         2.477       3                                                   36.97         2.431       3                                                   37.73         2.384       7                                                   ______________________________________                                    

EXAMPLE 12

For comparison purposes, Example 1 of U.S. Pat. No. 4,954,325,incorporated herein by reference, was repeated. The as-synthesizedcrystalline material of the Example, referred to herein as MCM-22precursor or the precursor form of MCM-22, was examined by X-raydiffraction analysis. Its X-ray diffraction pattern is presented inTable XV. The X-ray diffraction pattern of the calcined form of thismaterial (538° C. for 20 hours) is shown in Table XVI below, and in FIG.1 of U.S. Pat. No. 4,954,325.

                  TABLE XV                                                        ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        3.1           28.5       14                                                   3.9           22.7       <1                                                   6.53          13.53      36                                                   7.14          12.38      100                                                  7.94          11.13      34                                                   9.67          9.15       20                                                   12.85         6.89       6                                                    13.26         6.68       4                                                    14.36         6.17       2                                                    14.70         6.03       5                                                    15.85         5.59       4                                                    19.00         4.67       2                                                    19.85         4.47       22                                                   21.56         4.12       10                                                   21.94         4.05       19                                                   22.53         3.95       21                                                   23.59         3.77       13                                                   24.98         3.56       20                                                   25.98         3.43       55                                                   26.56         3.36       23                                                   29.15         3.06       4                                                    31.58         2.833      3                                                    32.34         2.768      2                                                    33.48         2.676      5                                                    34.87         2.573      1                                                    36.34         2.472      2                                                    37.18         2.418      1                                                    37.82         2.379      5                                                    ______________________________________                                    

                  TABLE XVI                                                       ______________________________________                                        Degrees       Interplanar                                                     2-Theta       d-spacing (A)                                                                            I/I.sub.o                                            ______________________________________                                        2.80          31.55      25                                                   4.02          21.98      10                                                   7.10          12.45      96                                                   7.95          11.12      47                                                   10.00         8.85       51                                                   12.90         6.86       11                                                   14.34         6.18       42                                                   14.72         6.02       15                                                   15.90         5.57       20                                                   17.81         4.98        5                                                   19.08         4.65        2                                                   20.20         4.40       20                                                   20.91         4.25        5                                                   21.59         4.12       20                                                   21.92         4.06       13                                                   22.67         3.92       30                                                   23.70         3.75       13                                                   25.01         3.56       20                                                   26.00         3.43       100                                                  26.96         3.31       14                                                   27.75         3.21       15                                                   28.52         3.13       10                                                   29.01         3.08        5                                                   29.71         3.01        5                                                   31.61         2.830       5                                                   32.21         2.779       5                                                   33.35         2.687       5                                                   34.61         2.592       5                                                   ______________________________________                                    

What is claimed is:
 1. A synthetic porous crystalline materialcharacterized by an X-ray diffraction pattern including valuessubstantially as follows:

    ______________________________________                                        Interplanar d-Spacing (A)                                                                          Relative Intensity                                       ______________________________________                                        13.15 ± 0.26      w-s (shoulder)                                           12.49 ± 0.24      vs                                                       11.19 ± 0.22      m-s                                                       6.43 ± 0.12      w                                                         4.98 ± 0.10      w                                                         4.98 ± 0.10      w                                                         4.69 ± 0.09      w                                                         3.44 ± 0.07      vs                                                        3.24 ± 0.06      w                                                        ______________________________________                                    

and having a composition comprising the molar relationship

    X.sub.2 O.sub.3 :(n)YO.sub.2,

wherein n is less than about 35, X is a trivalent element and Y is atetravalent element.
 2. The synthetic porous crystalline material ofclaim 1 characterized by an X-ray diffraction pattern including valuessubstantially as set forth in Table III of the specification.
 3. Thesynthetic porous crystalline material of claim 1 characterized by anX-ray diffraction pattern including values substantially as set forth inTable V of the specification.
 4. The synthetic porous crystallinematerial of claim 1 characterized by an X-ray diffraction patternincluding values substantially as set forth in Table VII of thespecification.
 5. The synthetic porous crystalline material of claim 1characterized by an X-ray diffraction pattern including valuessubstantially as set forth in Table IX of the specification.
 6. Thesynthetic porous crystalline material of claim 1 characterized by anX-ray diffraction pattern including values substantially as set forth inTable XI of the specification.
 7. The synthetic porous crystallinematerial of claim 1 characterized by an X-ray diffraction patternincluding values substantially as set forth in Table XIV of thespecification.
 8. The crystalline material of claim 1 wherein n is fromabout 10 to less than about
 35. 9. The crystalline material of claim 8wherein n is from about 15 to about
 31. 10. The crystalline material ofclaim 1 having a composition, on an anhydrous basis and in terms ofmoles of oxides per n moles of YO₂, expressed by the formula:

    (0.1-0.6)M.sub.2 O:(1-4)R:X.sub.2 O.sub.3 :nYO.sub.2

wherein M is alkali or alkaline earth metal and R is an organic moiety.11. The crystalline material of claim 10 wherein said R is selected fromthe group consisting of cycloalkylamine, azacycloalkane,diazacycloalkane, and mixtures thereof.
 12. The crystalline materialcomprising the crystalline material of claim 10 having original cationsreplaced, at least in part, with a cation or a mixture of cationsselected from the group consisting of hydrogen and hydrogen precursors,rare earth metals, and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB,IVB, VIB and VIII of the Periodic Table of the Elements.
 13. Thecrystalline material of claim 1 wherein X comprises aluminum and Ycomprises silicon.
 14. The crystalline material of claim 1 wherein Xcomprises gallium and Y comprises silicon.
 15. The crystalline materialof claim 8 wherein X comprises aluminum and Y comprises silicon.
 16. Thecrystalline material of claim 9 wherein X comprises aluminum and Ycomprises silicon.
 17. The crystalline material of claim 12 wherein saidreplacing cations comprise hydrogen or a hydrogen precursor.
 18. Thecrystalline material of claim 12 wherein said replacing cations comprisemetals.
 19. A composition comprising the crystalline material of claim 1and a matrix.
 20. The composition of claim 19 wherein said matrixcomprises alumina, silica, zirconia, titania, magnesia, beryllia or acombination thereof.
 21. A synthetic porous crystalline material havingthe X-ray diffraction pattern of FIG.
 2. 22. A synthetic porouscrystalline material having the X-ray diffraction pattern of FIG.
 5. 23.A synthetic porous crystalline material having the X-ray diffractionpattern of FIG.
 6. 24. A synthetic porous crystalline material havingthe X-ray diffraction pattern of FIG.
 7. 25. A process for converting afeedstock comprising hydrocarbon compounds to conversion product whichcomprises contacting said feedstock at conversion conditions with acatalyst comprising an active form of synthetic porous crystallinematerial characterized by an X-ray diffraction pattern including valuessubstantially as follows:

    ______________________________________                                        Interplanar d-Spacing (A)                                                                          Relative Intensity                                       ______________________________________                                        13.15 ± 0.26      w-s (shoulder)                                           12.49 ± 0.24      vs                                                       11.19 ± 0.22      m-s                                                       6.43 ± 0.12      w                                                         4.98 ± 0.10      w                                                         4.98 ± 0.10      w                                                         4.69 ± 0.09      w                                                         3.44 ± 0.07      vs                                                        3.24 ± 0.06      w                                                        ______________________________________                                    

and having a composition comprising the molar relationship

    X.sub.2 O.sub.3 :(n)YO.sub.2,

wherein n is less than about 35, X is a trivalent element and Y is atetravalent element.
 26. The process of claim 25 wherein said feedstockcomprises an olefin and said product comprises an aromatic.
 27. Theprocess of claim 26 wherein said feedstock comprises propylene.